EP0122442A1 - Composés d'acide pérylène-3,4,9,10-tétracarboxylique-monoanhydride-monoimide et monoimidazole, procédé pour leur préparation et leur application - Google Patents

Composés d'acide pérylène-3,4,9,10-tétracarboxylique-monoanhydride-monoimide et monoimidazole, procédé pour leur préparation et leur application Download PDF

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Publication number
EP0122442A1
EP0122442A1 EP84102555A EP84102555A EP0122442A1 EP 0122442 A1 EP0122442 A1 EP 0122442A1 EP 84102555 A EP84102555 A EP 84102555A EP 84102555 A EP84102555 A EP 84102555A EP 0122442 A1 EP0122442 A1 EP 0122442A1
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EP
European Patent Office
Prior art keywords
substituted
carbon atoms
alkyl
radical
alkoxy
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EP84102555A
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German (de)
English (en)
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EP0122442B1 (fr
Inventor
Ernst Dr. Spietschka
Helmut Dr. Tröster
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/06—Peri-condensed systems

Definitions

  • the invention is in the technical field of the production of dyes and pigments.
  • Perylene-3,4,9,10-tetracarboxylic acid monoanhydride monoalkyl imide compounds are already known from European Patent Application Publication No. 0 039 482-A, but corresponding monoimide monoanhydrides with weakly basic amines can be relied on as alkylamines not produce the process described there or only with difficulty and extremely low yields.
  • Alkyl groups of 1 to 4 carbon atoms are, for example, the methyl and the ethyl group; Alkoxy groups of 1 to 4 carbon atoms are, for example, the methoxy and the ethoxy group.
  • the substituents in the formula radical A can be 1, 2 or 3 substituents.
  • Preferred compounds of the general formula (1) are those in which Y is an oxygen atom and A the Is a phenyl radical which can be substituted by substituents from the group alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine, or in which Y represents a nitrogen atom and A denotes the o-phenylene radical, which can be substituted by one or two substituents from the group alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and chlorine.
  • the present invention further relates to a process for the preparation of the new compounds of the general formula (1), which is characterized in that the tetra salt of perylene-3,4,9,10-tetracarboxylic acid of the general formula (2) in which X and n have the meanings given above and M (+) is the ammonium ion of a secondary or preferably tertiary amine which has a pH in aqueous solution.
  • B represents the optionally substituted phenyl or pyridyl radical mentioned above for A
  • D represents the ortho-pbenylene radical which, as indicated above for A, by substituents from the group halogen, alkyl of 1 to 4 carbon atoms and Alkoxy of 1 to 4 carbon atoms can be substituted, in aqueous or aqueous-organic solution with each other and this reaction solution at room temperature or elevated temperature, such as at a temperature between 10 ° C and the boiling point of the reaction mixture, preferably between 15 and 95 ° C, first by adding acid, advantageously by gradual addition of acid, to a pH between 7 and 5, preferably between 6.8 and 6.2, and then the reaction within the specified pH range at elevated temperature, preferably at a temperature between 70 ° C and the boiling point of the reaction medium , as between 70 and 110 ° C.
  • reaction of the compounds of the general formula (2) with the amines of the general formula (3) or (4) is carried out using equimolar amounts, a slight excess of the amine (3) or (4) being appropriate. Depending on the amine used as the reaction component, in particular the basicity of the amine, this excess can be up to 20 mol%.
  • the aqueous-organic reaction medium contains, for example, dimethylformamide or an unsaturated tertiary amine, such as in particular a picoline or pyridine, as the organic solvent component.
  • an aqueous-organic reaction medium with a picoline or pyridine as the organic solvent component is a preferred one Embodiment.
  • These unsaturated tertiary amines can serve as buffers and solubilizers for the reaction component in the reaction mixture; the amount of this organic solvent component can be varied within wide limits.
  • 10 to 80% of the unsaturated tertiary amine is used, based on the amount of water used in the reaction solution.
  • the unsaturated tertiary amine is advantageously added to the aqueous reaction solution before the pH range between 7 and 5 is set.
  • the ammonium ion M (+) in the starting compounds of the general formula (2) is preferably an ammonium ion of the general formula (5) in which R 1 , R and R can have meanings which are the same or different from one another and R represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl group, which can be substituted by a hydroxyl group, R 2 is an alkyl group of 1 to 4 carbon atoms, such as the methyl or ethyl group, which can be substituted by a hydroxyl group, and R 3 is an alkyl group of 1 to 4 carbon atoms, such as the methyl or ethyl group, which can be substituted by a hydroxyl group, or in which R 2 and R 3 together with the nitrogen atom form a saturated, heterocyclic ring which optionally contains an oxygen atom or nitrogen atom as a further hetero atom.
  • R 1 , R and R can have meanings which are the same or
  • Corresponding secondary or tertiary amines suitable for this purpose are, for example, dimethylamine, diethylamine, dibutylamine, diethanolamine, Triethanolamine, trimethylamine, triethylamine, piperidine and morpholine, preferably thereof trimethylamine and in particular triethylamine.
  • Aromatic amines (3) which serve as starting compounds are, for example, aniline, 2-methyl-aniline, 3-methyl-aniline, 4-methyl-aniline, 3,5-dimethyl-aniline, 2,4-dimethyl-aniline, 2 , 5-dimethyl-aniline, 2,6-dimethyl-aniline, 3,4-dimethyl-aniline, 4-isopropyl-aniline, 2,4,6-trimethylaniline, 2-chloro-aniline, 3-chloro-aniline, 4 -Chloro-aniline, 2,4-dichloro-aniline, 3-bromo-aniline, 3-iodo-aniline, 2-methyl-5-chloro-aniline, 3-chloro-4-methyl-aniline, 3-trifluoromethylaniline, 3 , 5-bis (trifluoromethyl) aniline, 2-aminophenol, 3-aminophenol, 4-methoxy-aniline, 4-ethoxy-aniline, 2-amino-1,4-dimethoxy-benzene, 4-amin
  • Amino compounds of the general formula (4) which serve as starting compounds are, for example, 1,2-diaminobenzene, 4-methyl-1,2-diaminobenzene, 4-methoxy-1,2-diaminobenzene, 4-chloro-1,2-diaminobenzene and 4,5-dichloro-1,2-diaminobenzene.
  • the process according to the invention can be carried out, for example, by first adjusting the perylene tetracarboxylic acid or its dianhydride in water with the amount of the amino compound required for conversion into the tetracarboxylate, which has a pH of 8.5 or higher in water is treated in the usual way at elevated temperature.
  • a small excess is expediently used, such as up to 10% of the amine, ie up to 4.4 mol of this amine, based on one mol of perylene tetracarboxylic acid or dianhydride.
  • inorganic and organic acids can be used as acids, for example mineral acids such as hydrochloric acid or sulfuric acid, but preferably because of their buffering effect *) weak organic or inorganic acids such as formic acid, acetic acid, propionic acid, carbonic acid or phosphoric acid.
  • the mixture is then heated and the specified pH range is maintained by adding further acid, since the pH would otherwise rise during the reaction. * ) medium to
  • the reaction product formed is isolated in a conventional manner by acidifying the reaction mixture and filtration.
  • the alkali-insoluble diimide or bisbenzimidazole compound formed can be removed by adding alkali and by filtration. Any unconverted perylene tetracarboxylic acid that may still be present can be separated from the usually poorly soluble potassium salt of the end product according to the invention via its readily soluble tetrakalium salt.
  • novel compounds of the general formula (1) according to the invention represent valuable starting products for the preparation of colorants (dyes and pigments), such as symmetrical or * ) N-substituted perylene-3,4,9,10-tetracarboxylic acid diimides + ).
  • colorants dye and pigments
  • they can also be used, if appropriate after appropriate conditioning, as colorants, for example in paints or for coloring polymers, such as polyolefins and polyvinyl chloride.
  • *) asymmetrical +) see, for example, Chemistry Letters 1979, 151-154
  • the following examples serve to explain the invention in more detail.
  • the parts are parts by weight and the percentages are percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume like the kilogram to the liter.
  • the procedure is as follows: the moist filter cake is stirred in 1500 parts of 5% strength aqueous potassium hydroxide solution at 90 to 95 ° C. for two hours, then suction filtered at 20 to 25 ° C. and with 5% strength aqueous solution Potash lye washed until the filtrate runs out colorless. The filter cake is then treated with hot water, the dipotassium salt of perylene tetracarboxylic acid mono- (3,5-dimethylphenyl ⁇ imide dissolving with a deep red-violet color.
  • the insoluble diimide is separated off by filtration, the compound according to the invention is precipitated and isolated by acidifying the filtrate.
  • Example 1 The procedure described in Example 1 is followed, but the appropriate amount of concentrated aqueous hydrochloric acid is used instead of the phosphoric acid to adjust the pH.
  • the product according to the invention is obtained in a similarly good quality in a yield of 40% of theory.
  • Example 2 The procedure described in Example 1 is followed, but the corresponding amount of acetic acid is used instead of the phosphoric acid to adjust the pH.
  • the compound of the invention is obtained in equally good quality in a yield of 61% of theory.
  • Example 1 The compound of the invention given in Example 1 is obtained in the same quality in a yield of 89.9 parts (corresponding to 90.8% of theory).
  • a solution of the tetrammonium salt of 39.2 parts of perylene-3,4,9,10-tetracarboxylic acid dianhydride and 38.3 parts of morpholine in 400 parts of water prepared at 90 ° C. is mixed with a solution of 13.3 parts of 3,5-dimethyl aniline combined in 200 parts by volume of pyridine. About 40 parts of acetic acid are added to this reaction mixture at 90 ° C. in the course of 6 hours to establish and maintain a pH range from 7 to 6.
  • the monoxylidide according to the invention is obtained in approximately the same good quality and a yield of 81.8% of theory.
  • Example 3 If the procedure described in Example 3 is followed, but using the tetrapiperidinium or tetra (trimethylammonium) salt instead of the tetramorpholinium salt of perylene tetracarboxylic acid, the formula I according to the invention given in Example 1 is obtained Monoxylidide in the same good quality and about the same high yield.
  • a solution of 20.5 parts of aniline in 200 parts by volume is added to a solution of 78.4 parts of perylene-3,4,9,10-tetracarboxylic acid dianhydride prepared at 80 ° C. in 740 parts of water and 100 parts of 40% aqueous dimethylamine -Picolin run up.
  • a pH of 6.5 is then established by adding 85% aqueous phosphoric acid and the reaction is carried out by heating at 90 ° C for 3 hours while maintaining a pH range of 6 , 7 to 6.3 over.
  • a solution of the tetra (triethylammonium) salt of the prepared from 196 parts of perylene-3,4,9,10-tetracarboxylic dianhydride, 2000 parts of water and 222 parts of triethylamine Perylene tetracarboxylic acid is mixed with 1000 parts by volume of pyridine and then with 75.5 parts of 4-ethoxy-aniline and heated to 90 ° C.
  • the initial pH is adjusted from 8.2 to 7.0 with about 40 parts of acetic acid and added over a period of 6 hours
  • composition of the compound according to the invention corresponds to the general formula (1a) given in Example 4, in which R represents the p-ethoxyphenyl radical.
  • a triethylammonium salt solution of perylene-3,4,9,10-tetracarboxylic acid prepared according to Example 2 is, after adding a solution of 27.0 parts of 4-methoxy-aniline in 100 parts by volume of pyridine at a temperature of 20 to 25 ° C with 78 parts 85% aqueous phosphoric acid added; the pH value drops from initially 9.8 to 6.3.
  • the yellow suspension obtained is heated to 90 ° C. and the reaction is continued for a further hour at this temperature, the pH still initially falling to about 5.5 and then rising again to a pH of about 6.5.
  • Example 2 To prepare a compound according to the invention, the procedure described in Example 2 is followed, except that 24.0 parts of 2-aminophenol are used as the starting component instead of 3,5-dimethylaniline.
  • the compound according to the invention produced here has the following constitution:
  • This compound according to the invention has the following constitution:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
EP84102555A 1983-03-14 1984-03-09 Composés d'acide pérylène-3,4,9,10-tétracarboxylique-monoanhydride-monoimide et monoimidazole, procédé pour leur préparation et leur application Expired EP0122442B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3309060 1983-03-14
DE19833309060 DE3309060A1 (de) 1983-03-14 1983-03-14 Perylen-3,4,9,10-tetracarbonsaeure-monoanhydrid-monoimid- und -monoimidazolid-verbindungen, verfahren zu ihrer herstellung und ihre verwendung

Publications (2)

Publication Number Publication Date
EP0122442A1 true EP0122442A1 (fr) 1984-10-24
EP0122442B1 EP0122442B1 (fr) 1987-11-19

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EP84102555A Expired EP0122442B1 (fr) 1983-03-14 1984-03-09 Composés d'acide pérylène-3,4,9,10-tétracarboxylique-monoanhydride-monoimide et monoimidazole, procédé pour leur préparation et leur application

Country Status (4)

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US (1) US4594420A (fr)
EP (1) EP0122442B1 (fr)
JP (1) JPS59176352A (fr)
DE (2) DE3309060A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5154770A (en) * 1984-10-03 1992-10-13 Hoechst Aktiengesellschaft Mix-crystal pigments based on perylenetetracarbimides, process for their preparation and their use
WO1999031069A1 (fr) * 1997-12-15 1999-06-24 Ciba Specialty Chemicals Holding Inc. Acides perylene-imide-monocarboxyliques utilises comme colorants

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3513358A1 (de) * 1985-04-15 1986-10-16 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von perylen-3,4,9,10-tetracarbonsaeurearylimiden
DE3535496A1 (de) 1985-10-04 1987-04-16 Bayer Ag Verfahren zur fluoreszenzloeschung und neue kationische naphthalin-peri-dicarbonsaeureimid-derivate
US6986811B2 (en) * 2003-01-31 2006-01-17 Basf Aktiengesellschaft Perylene derivatives and their application as dispersants
WO2005078023A2 (fr) * 2004-02-11 2005-08-25 Basf Aktiengesellschaft Pigments de perylene noirs
CN100445283C (zh) * 2006-11-22 2008-12-24 天津大学 光响应性偶氮苯-苝酰亚胺化合物的制备方法
JP5151192B2 (ja) * 2007-03-09 2013-02-27 Ｊｎｃ株式会社 ペリレン誘導体およびそれを用いた光電変換素子
US8530270B2 (en) * 2010-04-30 2013-09-10 Eastman Kodak Company Methods of preparing semiconductive compositions and devices
US9287419B2 (en) 2011-01-05 2016-03-15 Nitto Denko Corporation Wavelength conversion perylene diester chromophores and luminescent films
WO2013049062A2 (fr) 2011-09-26 2013-04-04 Nitto Denko Corporation Chromophores hautement fluorescents et photo-stables permettant une plus grande efficacité de récupération de l'énergie solaire
WO2013052381A2 (fr) 2011-10-05 2013-04-11 Nitto Denko Corporation Film de conversion de longueur d'onde ayant une couche adhésive sensible à la pression pour améliorer le rendement de collecte solaire
CN116285221B (zh) * 2023-03-31 2024-03-22 米库玻璃纤维增强塑料泰州有限责任公司 一种玻璃纤维增强改性环氧树脂及其制备方法

Citations (2)

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Publication number Priority date Publication date Assignee Title
FR2456102A1 (fr) * 1979-05-10 1980-12-05 Vorozhtsov Georgy Derives d'acide 1,1' -binaphtyl-4,4', 5,5', 8,8' -hexacarboxylique, leur procede de preparation et leurs applications a la teinture et l'impression de materiaux textiles
EP0039482A2 (fr) * 1980-05-05 1981-11-11 Hoechst Aktiengesellschaft Monoanhydride-monoimides de l'acide pérylène-3,4,9,10-tétracarboxylique, procédé pour leur préparation et leur utilisation

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US1924090A (en) * 1930-09-05 1933-08-29 Gen Aniline Works Inc Mono-molecular condensation product of 1.4.5.8-naphthalene-tetra-carboxylic acid andalpha process of preparing it
DE2237539C3 (de) * 1972-07-31 1981-05-21 Hoechst Ag, 6000 Frankfurt Elektrophotographisches Aufzeichnungsmaterial

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2456102A1 (fr) * 1979-05-10 1980-12-05 Vorozhtsov Georgy Derives d'acide 1,1' -binaphtyl-4,4', 5,5', 8,8' -hexacarboxylique, leur procede de preparation et leurs applications a la teinture et l'impression de materiaux textiles
EP0039482A2 (fr) * 1980-05-05 1981-11-11 Hoechst Aktiengesellschaft Monoanhydride-monoimides de l'acide pérylène-3,4,9,10-tétracarboxylique, procédé pour leur préparation et leur utilisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts Band 91, Nr. 4, 23. Juli 1979, Columbus, Ohio, USA Y. NAGAO et al. "Synthesis of unsymmetrical perylenebis(dicarboximide) derivatives", Seite 93, Spalte 1, Abstract Nr. 22404r & Chem. Lett., Nr. 2, 1979, Seiten 151-154 *
Chemical Abstracts Band 93, Nr. 26, 29. Dezember 1980, Columbus, Ohio, USA Y. NAGAO et al. "Synthesis and reactions of perylenecarboxylic acid derivatives. 4. Syntheses and properties of unsymmetrical 3,4:9,10-perylenebis(dicarboximide) derivatives", Seite 91, Spalte 1, Abs *
Chemical Abstracts Band 97, Nr. 11, 13. September 1982, Columbus, Ohio, USA G.N. VOROZHTSOV et al. "Derivatives of 1,1'-binaphthyl. IX. Formation of derivatives of 3,4,9,10-perylenetetracarboxylic acid in the electrochemical reduction of 8,8'-disubstituted derivatives of 1,1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5154770A (en) * 1984-10-03 1992-10-13 Hoechst Aktiengesellschaft Mix-crystal pigments based on perylenetetracarbimides, process for their preparation and their use
WO1999031069A1 (fr) * 1997-12-15 1999-06-24 Ciba Specialty Chemicals Holding Inc. Acides perylene-imide-monocarboxyliques utilises comme colorants
US6166210A (en) * 1997-12-15 2000-12-26 Ciba Specialty Chemicals Corporation Perylene imide monocarboxylic acids

Also Published As

Publication number Publication date
JPH0458506B2 (fr) 1992-09-17
JPS59176352A (ja) 1984-10-05
DE3467578D1 (en) 1987-12-23
EP0122442B1 (fr) 1987-11-19
US4594420A (en) 1986-06-10
DE3309060A1 (de) 1984-09-20

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